Braided hollow fiber membranes are commonly used in modules containing from several hundred to several thousand membranes. Damage to a single membrane in a module, which damage results in dirty water contaminating the permeate, is a serious problem which occurs more often than desired. Though the permeate is typically water, the permeate may be any filterable liquid to be separated from a suspension or dispersion of finely divided particles in the liquid.
To date, numerous braided membranes have been disclosed, each of which purports to provide desirable filtration efficiency but offer scant useful knowledge relating to avoiding the damage to a membrane or maximizing permeate efficiency. Emphasis on physical strength of the membrane is embodied in disclosures of U.S. Pat. Nos. 3,644,139; 4,061,821; 5,472,607; 5,914,039; 6,354,444; 7,165,682; 7,172,075; 7,306,105; 7,861,869; 7,909,172 and others. The requirement of strength decreed that these prior art braids be made by braiding multiple yarns, each comprising lengths of multiple monofilaments (or “filaments” for brevity). The drawbacks of using multifilament yarns were either overlooked or ignored.
Membranes such as are disclosed in U.S. Pat. No. 4,061,821 to Hyano et al, (hereafter '821) have braid embedded beneath a thick polymer film to provide a stabilizing effect during use of the membrane. The term “embedded” as used herein describes yarn or monofilament with at least 99% of its surface coated with polymer. Braid having an inner diameter in the range of 0.5-10 mm and unspecified “thin thickness” is made from filaments overlying and randomly overlapping one and another (see FIGS. 4, 5 & 6 in '821) in multiple layers but are preferably made from multifilament yarn. The stabilizing effect of the openings in the reinforcing material was lost (see sentence beginning at the bottom of col 4, and bridging cols 4 and 5) when the braid was coated with polymer, so that their reinforced membrane was not an effective membrane.
The problem of stability was addressed in U.S. Pat. No. 5,472,607 to Mahendran et al, (hereafter '607) which teaches a film having a wall thickness in the range from 0.01 mm to 0.1 mm, supported on the outer circumferential surface of a preshrunk braid; a major portion of the area of the circular cross-section of the porous tubular support, viewed along the longitudinal central axis, is free from film and not embedded in film. Thus, it was not known how embedding the braid in the film affected the performance of the membrane; nor was it established whether failing to embed the braid in the film provided a significant advantage.
Membranes such as are disclosed in U.S. Pat. No. 6,354,444 to Mahendran et al, (hereafter '444) are produced by first weaving a tubular braid of multifilament yarn to have a cylindricity>0.8, preshrinking the braid, then coating the outer circumferential surface of the cylindrical braid with a dope of polymerizable membrane-forming polymer. The term “cylindricity” (sometimes referred to as “roundness”) refers to how perfectly the circular cross-section of the tubular support matches the geometry of a true circle drawn to correspond to the mean diameter of the braid, a perfect match being 1.0. By “weaving” is meant that the filaments are interlaced without being knotted (as they would be if the braid was knit). “Dope” refers to fluid “membrane polymer”, e.g. poly vinylidene fluoride (“PVDF”) whether molten or in a solution. If in solution and coagulated, the dope forms a film having a wall thickness of >0.2 mm and with desired attributes for the filtration of fluid to be filtered, typically dirty water. The '444 braid is relatively dense, having an air permeability in the range of from 1 to 10 cc/sec/cm2 at 1.378 kPa so that the voids in the braid are small enough to provide substantial resistance to the passage of air, and thus inhibit substantial penetration of polymer. The braid is preshrunk to provide stability of the braid. Yarn lying in a generally longitudinal orientation (along the z-axis) provides extension at break of the uncoated braid of at least 10% which extensibility is referred to as “give”.
The weave of the '444 braid is a circularly woven tubular braid. Such braids are tightly woven with at least one circumferential yarn lying in a generally x-y plane (z axis is longitudinally axial). This orientation necessarily constricts and prevents radial distension of the braid, but the preshrunk braid does have “give” in the longitudinal direction. However, when the braid is coated with a relatively elastic polymer to form the membrane, it is essentially longitudinally non-extensible (along the z-axis). In other words, the '444 membrane, whether pulled in the axial direction or pressured from within during backwashing, has essentially no “give”. The importance of “give” relates particularly to effective backwashing. The higher the backwashing pressure the better, if it does not damage the membranes, because such pressure allows faster and more effective cleansing of contaminated membranes and therefore provides an economic advantage.
Because the '444 braid is deliberately not embedded in the polymer, yarn defining the lumen (bore) of the membrane is not coated with polymer. Other references disclose braids woven to minimize the problem of too-deep penetration of the polymer film. The non-embedded yarn, in all such instances, is prone to damage such as pin-holes. Such damage lessens the initial high bubble point of the freshly deployed membrane. The “bubble point” refers to the pressure under which a stream of air escapes through the largest pore in a wall of a wetted, defect-free membrane which has desirable flux. Further, the importance of stability of the structure of the braid during operation, particularly the effect of shrinkage, was not known.
Though U.S. Pat. No. 7,861,869 discloses a semipermeable capillary membrane reinforced by a braid of monofilament yarn, the yarn is made by bundling multiple monofilaments (36 in example 1). The braid is not made by braiding separate monofilaments. Penetration of the dope into the braid is controlled so that the inner channel (lumen) of the braid is not blocked. The process taught herein prepares an “outer skinned” version of the reinforced membrane, explicitly avoiding embedding the braid.
WO-A-0397221A1 describes a tubular fiber membrane which is longitudinally reinforced by unbraided yarns, not by a braid. The axial bore is formed by injecting an internal coagulation solution in the centre but the thickness of the annular film defining the lumen cannot be controlled.
US 2009/0206026 A1 to Yoon et al, titled “External pressure type hollow fiber membrane having reinforcing supporter with monofilament for gas separation and water treatment, and method and apparatus for preparing the same” states: “The hollow fiber membrane of the present invention has excellent pressure resistance and high tension force by using the rigid and tubular supporter, an improved softness by using the monofilaments, and an increased bonding force between the supporter and the coating layer by increasing the concave-convexo degree of the reinforcing supporter.” (see '026 Abstract, lines 6-11). That the tubular supporter in the described hollow fiber membrane is rigid, is reiterated under “Industrial Capability” (see line 3 of paragraph [0057]. Such rigidity serves to distinguish the '026 membrane over the membrane of '607 to Mahendran et al, discussed in '026 as being the most relevant reference which teaches that “The support itself is so flexible (flaccid) that it does not have a circular cross-section and collapses with finger pressure.” (see Abstract, lines 4-6) “By “flaccid” is meant that the denier of monofilaments used in the yarns or “ends” for carriers which are braided, and the number of picks/unit length of the braid, are such that a tubular braid has very little mechanical strength in a vertical plane normal to its longitudinal central axis, so that it is so flexible that it can be easily manually tied into a knot. A typical braid starts out as multiple filaments which make up a single “end” and two “ends” are plied together in 3.8 twists/25.4 mm to make up a yarn or “carrier”. Multiple carriers, preferably 24, are used to braid a tubular braid.” (see '607, col 3 lines 24-33). Clearly, the '026 statement relating to a rigid and tubular supporter are meant to distinguish over the '607 braid.
Note that though FIGS. 4 and 5 in '026 purport to be photomicrographs of the reinforcing supporter, both woven with monofilaments of 130 deniers and of 32 and 24 yarns respectively, other than stating that the diameter of the supporter can be controlled according to the number of cones (see [0042]), there is no indication in either photomicrograph as to the diameter of the woven braids shown. Neither is there any identification, anywhere, either of the weave, or of the machinery, used to make a braid having any specified diameter, much less a nominal inside diameter in the range from about 1.0 mm (to make a membrane having a nominal outer diameter of 1.5 mm, depending upon the denier of the monofilament to be used), to about 2.5 mm (to make a membrane having a nominal outer diameter of 3.0 mm, depending upon the denier of the monofilament to be used), as specified for the braid and membrane claimed herein. In particular, there is no mention of using a flexible cable, dissolvable in an aqueous solution (referred to as “aqueous-dissolvable”) upon which to weave the braid. By “nominal” is meant “average”.
Particularly noteworthy is that the '026 membrane is woven with both, monofilament and multifilament yarns; this provides convincing evidence that the inventors of the '026 braid failed to realize that “whiskering” and “fuzz” were the root causes of failure in membranes with multifilament braids.
In FIG. 6 of '026 there is illustrated an automatic device in which a perforated wire 2 extends along the central vertical axis of an injector for an internal coagulating solution 4. A high pressure injection nozzle 3 injects the internal coagulating solution onto the wire, and the solution is also squirted through the perforations while the reinforcing supporter passes over and is forwarded by the roller 5 in contact with the wire 2. (see [0045]).
Aside from the problem of perforating about a 2.0 mm diameter wire, doing which is beyond the skill of the inventors herein, it will be seen in the test presented in example 1 below, that an open weave tubular braid having the diameter claimed herein, made with woven monofilament in the size range claimed herein, cannot be forwarded (or “passed”) over a wire as described in '026 because the friction is too great, and other reasons. Numerous attempts to forward a tubular braid of monofilaments only (see example 1 below) to make a membrane in the range of nominal outer diameters from 1.5-3.0 mm, fails to produce a usable, undistorted, uniform membrane. The '026 reference is therefore a non-enabling disclosure. Moreover, manually pulling the braid over the wire after the braid is coated with coagulant polymer, results in destruction of the membrane, again, because of the flaccid membrane and its excessive friction. To make and use the membrane claimed in '026 would require undue experimentation.
US 2004/0197557 to Eshraghi et al teaches (a) providing a molten removable substrate material in the form of an extrudate of a molten polymeric material (see [0011] to make a hollow fiber membrane having a dissolvable core, and the use of reinforcing fibers as follows: “Additionally, one or more reinforcing fibers can be incorporated into such polymeric membrane to form a fiber-reinforced tubular polymeric membrane structure. Preferably, such reinforcing fibers extend continuously along the longitudinal axis of the fibrous core or substrate and therefore provide axial reinforcement to the hollow fibrous membrane. Fiberglass having an average diameter of about 0.1-500 μm is particularly suitable for practice of the present invention, while other fibrous materials, including but not limited to carbon fibers, metal fibers, resin fibers, and composite fibers, can also be employed for reinforcing the hollow fibrous membrane. The reinforcing fiber can either be co-extruded with one of the polymeric membrane-forming layers, or be encapsulated between two polymeric membrane-forming layers, to form an integral part of the hollow fibrous membrane.” (see [0085]) There is no suggestion, beyond the statement that “such reinforcing fibers extend . . . hollow fibrous membrane” how one or more reinforcing fibers are to be incorporated into the polymeric membrane.
The '557 publication states “the solid core fiber itself is formed of a solid-phase removable substrate material, and at least one layer of a polymeric membrane-forming material is coated directly onto such solid core fiber.” (See [0023]). It thereafter states: “the molten removable substrate material is co-extruded with the membrane-forming polymer. (See [0041]-[0047]).
It is clear that Eshraghi et al did not extrude PVA because it degrades before it can be melt-extruded, irrespective of what grade of PVA is used. As evident in example 2 below, attempts were made to extrude each of three grades of PVA available from Kuraray, namely fully hydrolyzed (F-05 and F-17); intermediate hydrolyzed (M-17); and partially hydrolyzed (P-24, P-20, P-17 and P-05). The temperature at which each of the polymers degrades is lower than its softening temperature. Therefore each attempt resulted in severe degradation of each.
In the description of the process illustrated in FIG. 3A, the '557 publication states “a string or a tow of removable core fiber 122 from a spool 120 is passed through the extrusion die 124. A thin layer of the viscous polymeric solution 101 is therefore applied onto the removable core fiber 122, forming a coated fiber 132.” ([See 0086]) The core fiber 122 could not have been flexible PVA as it necessarily would have to be plasticized with just sufficient plasticizer to provide a core fiber which was not degraded.
A core made from PVA in a solution of hot water has insufficient strength to maintain its cylindrical form—discovered to be a critical requirement for making the open weave braid of this invention. Not being able to make a PVA core negated the suggestion in '557 that PVA may be used for the core.
As for the reinforcing the '557 publication states “The reinforcing fiber can either be co-extruded with one of the polymeric membrane-forming layers, or be encapsulated between two polymeric membrane-forming layers, to form an integral part of the hollow fibrous membrane.” There is no suggestion that the extrudate be covered with a braid before being coated with membrane polymer, and no way this could be accomplished using the teachings of their disclosure.
In a manner analogous to that stated above, commercially available ethyl vinyl alcohol (EVOH) from Kuraray; commercially available polylactic acid from Nature Works; commercially available nylons from Shakespeare; and no-longer commercially available copolyester from Eastman, failed to produce a usable core despite numerous trials in each of which the conditions of extrusion were changed.
Clearly the disclosure of the '557 publication is not an enabling disclosure.
With respect to the use of monofilaments, apart from a braid thereof, the '557 publication provides no indication that it recognized the ill effects of “whiskering” and “fuzz” in a braid made with at least some multifilament yarns.
Neither did the '557 publication recognize that only a tubular braid embedded near the inside diameter of the membrane so as to reinforce the lumen provided the highest peel strength, bubble point and permeate efficiency. There is no suggestion that a braid be woven using only monofilaments woven in a particular way, namely with an open weave so as to avoid having circumferentially restricting filaments which would not have “give” under abnormally high backwashing pressure.
Publication No. WO/2010/148517 to Cote et al (hereafter the “'517 publication”) presents the concept of using a “dissolvable filament (solid or hollow) core” to make a hollow fiber membrane (see [0040]). It states that “the core can be a solid or capillary tube can be later dissolved in a solvent, preferably the solvent used to coagulate the membrane (typically water). Examples of water-soluble polymers include PVA, EVOH (made by Kuraray), as well as some forms of polyester (available from Eastman) and nylon (available from Shakespeare).” (see [0065]). Not mentioned is high amorphous vinyl alcohol (HAVOH) and more commonly available polylactic acid (PLA), cellulose acetate, hydroxyethyl cellulose, polyethylene oxide (PEO) and polyethylene glycol (PEG), all of which are water-soluble. If he had used PVA as a removable core, he would have realized that despite extended washing with water, more than 10% of the usable pores in the lumen of the membrane remain clogged, and the membrane requires a wash with an aqueous solvent in which the PVA is far more soluble than in water. They would have disclosed such a complex cleaning requirement.
The Problem:
Currently used braided multifilament membranes are more readily susceptible to damage than they should be, resulting in leakage. The inventors herein discovered that such damage, resulting in leaks, typically occurs at vulnerable “thin spots” where yarns overlap near the surface of the braid; further, that such overlap of multifilament yarns or broken yarn is also conducive to formation of “whiskers” or “fuzz” which initiates pin-hole leaks, resulting in a low bubble point. Since in the '444 patent, thin film is deliberately restricted to the upper portion of the tubular braid, the uncoated lumen is formed and reinforced with unprotected, braided yarn, prone to whiskering. Such yarn tends to trap contaminant particles entering with the backwash and broken whiskers contaminate the permeate.
Still further, the relatively greater thickness of multifilament braid, relative to the thin film of polymer overlying the surface of the braid, results in a non-uniform thin polymer film having poor adhesion and a variable, low peel strength. In those instances where the lumen of the braid is deliberately coated with polymer film, the annular thickness of polymer film is uncontrollable (as evident in the '607, '869 and '075 patents inter alia). Though the '517 publication presented the concept of using a dissolvable polymer core such as PVA, what remained to be discovered was (i) how to overcome the degradation problem of PVA, yet make a reliably uniform core, (ii) how to make a flexible non-degraded PVA core which is strong enough to withstand the forces required to make an open weave braid snugly supported on the core, (iii) how to overcome the problem of dissolving the PVA core within a reasonably short time, and (iv) how to ensure that upon solving the prior two problems, the resulting membrane would have unclogged pores. Clogged pores would greatly diminish the permeate efficiency of the membrane. The goal was to obtain higher permeate efficiency than that obtained with multifilament reinforced membranes, and to remedy the aforementioned problems of braided membranes exemplified by the '517, and '444 membranes.